Synthesis and characterization of some new complexes of the Vaska-type trans-[IrX(CO)L2] (XCl or I; L=phosphite, phosphinite or phosphonite) and the direction of dihydrogen addition to these species
✍ Scribed by Luo Xiao-Liang; Demetrius Michos; Robert H. Crabtree; Michael B. Hall
- Publisher
- Elsevier Science
- Year
- 1992
- Tongue
- English
- Weight
- 827 KB
- Volume
- 198-200
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
A series of new Vaska-type complexes fmns-[IrX(CO)LJ (X=Cl, L=P(OEt)Ph, (l), P(OEt)zPh (Z), P(O-o-CJ&Ph), (3), P(OPri)3 (4), P(OBu")a (5); X=1, L=P(OEt)Phz (6), P(OEt)*Ph (7), P(O-o-C&Ph)3 (S), P(OBU")~ (9) are prepared and characterized. In solution complex 8 undergoes slow cyclometallation to give [IrHI(CO){P(Oo-C,H,Ph)(O-o-C&Ph)3(P(O_oC,H,Ph),}] (10). The oxidative addition of H, to l-9 occurs stereospecitically with cb addition of HZ parallel to the X-Ir-CO axis rather than perpendicular to the axis, leading to cis, trans-[IrH,X(CO)b]
with a trans disposition of the two L ligands. This direction of HZ addition is not in agreement with a prior suggestion based on ab initio quantum chemical calculations.